Blowing agents for forming foam comprising unsaturated fluorocarbons

1. An open cell, closed cell or multimodal cell polyisocyanate-based foam prepared by reacting at least one organic polyisocyanate with at least one polyol in the presence of a blowing agent, wherein said blowing agent comprises a fluorocarbon or hydrofluorocarbon selected from the group consisting of:

(i) a hydrofluorocarbon having the formula E- or Z—R 1 CH═CHR 2 , wherein R 1 and R 2 are, independently, C 1 to C 6 perfluoroalkyl groups; and

(ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF 3 CF═CHCF 3 , CF 3 CH═CHCF 3 , CHF 2 CH═CHCF 3 , (CF 3 ) 2 C═CHCF 3 , CF 3 CF═CHCF 2 CF 3 , CF 3 CH═CFCF 2 CF 3 , (CF 3 ) 2 CFCF═CHCF 3 , CF 3 CF═CFCH 3 , CH 3 CF═CHCF 3 , CHF 2 CF═CFCF 2 CF 3 , CF 3 CF═CFCF 2 CHF 2 , CF 3 CF═CFCHFCF 3 , CF 3 CF═C(CF 3 )(CH 3 ), CH 2 FCH═C(CF 3 ) 2 , CH 3 CF═C(CF 3 ) 2 , (CF 3 ) 2 C═CHC 2 F 5 , (CF 3 ) 2 CFCF═CHCF 3 , (CF 3 ) 2 C═C(CH 3 )(CF 3 ), CF 3 CF═C(CH 3 )CF 2 CF 3 , CF 3 CH═CHCH(CF 3 ) 2 , (CF 3 ) 2 C═CHCF 2 CH 3 , CF 3 CF 2 CF═CFC 2 H 5 , CF 3 CF═CHCH(CF 3 )(CH 3 ), (CF 3 ) 2 C═CFC 2 H5, cyclo-CF 2 CF 2 CF 2 CH═CH—, cyclo-CF 2 CF 2 CH═CH—, CF 3 CF 2 CF 2 CH═CHCH 3 , cyclo-CF 2 CF 2 CF═CF—, cyclo-CF 2 CF═CFCF 2 CF 2 —, cyclo-CF 2 CF═CFCF 2 CF 2 CF 2 , CF 3 CH═CHCF 2 CF 3 , CF 3 CF 2 CH═CHCF 2 CF 3 , CF 3 CH═CHCF 2 CF 2 CF 3 , CF 3 CH═CFCF 2 CF 2 C 2 F 5 , CF 3 CF═CHCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CH═CFCF 2 C 2 F 5 , CF 3 CF 2 CF═CHCF 2 C 2 F 5 , C 2 F 5 CF 2 CF═CHCH 3 , C 2 F 5 CF═CHCH 3 , (CF 3 ) 2 C═CHCH 3 , CF 3 C(CH 3 )═CHCF 3 , CHF 2 CF═CFCF 3 , CH 2 FCF═CFCF 3 , CHF 2 CH═CFCF 3 , CF 3 CH═CFCHF 2 , CHF 2 CF═CFCHF 2 , CH 2 CF═CFCF 3 , CH 2 FCH═CFCF 3 , CF 3 CH═CFCH 2 F, —CHF 2 CF═CHCHF 2 , CF 3 CF═CHCH 3 , CF 3 CBr═CFCF 3 , CH 3 CBr═CHCF 3 , CF 3 CBr═CHCH 3 , CF 3 CF═CBrCF 2 CF 3 , E-CHF 2 CBr═CFC 2 F 5 , Z—CHF 2 CBr═CFC 2 F 5 , (CF 3 ) 2 CFCBr═CH 2 , CHBr═CF(CF 2 ) 2 CHF 2 , and (CF 3 ) 2 C═CHCH 2 Br,

and wherein the global warming potential of said blowing agent is less than 100, and wherein the solubility of said blowing agent in said polyol is such that they form an emulsion when mixed.

2. The open cell, closed cell or multimodal cell foam of claim 1 , wherein the foam has an overall density of from about 10 to about 500 kg/m 3 .

3. The open cell, closed cell or multimodal cell foam of claim 1 , wherein the foam has an overall density of from about 18 to about 100 kg/m 3 .

4. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said blowing agent is selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , E-CF 3 CF═CFCF 3 , Z—CF 3 CF═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 , and said blowing agent is present in a range of from about 1 to about 50 wt. %, based on the total weight of polyol and blowing agent.

5. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 4 , wherein said blowing agent is present in a range of from about 1 to about 25 wt. %, based on the total weight of polyol and blowing agent.

6. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein the foam is an open cell foam and the blowing agent comprises a hydrofluorocarbon selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 .

7. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein the foam is a multi-modal cell foam and the blowing agent comprises a hydrofluorocarbon selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , E-CF 3 CF═CFCF 3 , Z—CF 3 CF═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 .

8. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein the cell size, excluding voids, is about 200-300 microns (g).

9. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said foam has an initial insulation value (R) of at least 2.0/inch (thermal conductivity of 72.1 milliW/mK).

10. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said foam has an initial insulation value (R) of at least 4.0/inch (thermal conductivity of 36 milliW/mK).

11. An open cell, closed cell or multimodal cell thermoplastic foam prepared by foaming a foamable composition in the presence of a blowing agent which is stable under extrusion conditions, wherein said blowing agent comprises a fluorocarbon or hydrofluorocarbon selected from the group consisting of:

a hydrofluorocarbon having the formula E- or Z—R 1 CH═CHR 2 , wherein R 1 and R 2 are, independently, C 1 to C 6 perfluoroalkyl groups; and

(ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF 3 CF═CHCF 3 , CF 3 CH═CHCF 3 , CHF 2 CH═CHCF 3 , (CF 3 ) 2 C═CHCF 3 , CF 3 CF═CHCF 2 CF 3 , CF 3 CH═CFCF 2 CF 3 , (CF 3 ) 2 CFCF═CHCF 3 , CH 2 FCF═CFCHF 2 , CF 3 CF═CFCH 3 , CH 3 CF═CHCF 3 , CHF 2 CF═CFCF 2 CF 3 , CF 3 CF═CFCF 2 CHF 2 , CF 3 CF═CFCHFCF 3 , CF 3 CH═C(CF 3 ) 2 , CF 3 CF═C(CF 3 )(CH 3 ), CH 2 FCH═C(CF 3 ) 2 , CH 3 CF═C(CF 3 ) 2 , (CF 3 ) 2 C═CHC 2 F 5 , (CF 3 ) 2 CFCF═CHCF 3 , (CF 3 ) 2 C═C(CH 3 )(CF 3 ), CF 3 CF═C(CH 3 )CF 2 CF 3 , CF 3 CH═CHCH(CF 3 ) 2 , (CF 3 ) 2 C═CHCF 2 CH 3 , CF 3 CF 2 CF═CFC 2 H 5 , CF 3 CF═CHCH(CF 3 )(CH 3 ), (CF 3 ) 2 C═CFC 2 H 5 , cyclo-CF 2 CF 2 CF 2 CH═CH—, cyclo-CF 2 CF 2 CH═CH—, CF 3 CF 2 CF 2 CH═CHCH 3 , cyclo-CF 2 CF 2 CF═CF—, cyclo-CF 2 CF═CFCF 2 CF 2 —, cyclo-CF 2 CF═CFCF 2 CF 2 CF 2 , CF 3 CH═CHCF 2 CF 3 , CF 3 CF 2 CH═CHCF 2 CF 3 , CF 3 CH═CHCF 2 CF 2 CF 3 , CF 3 CF═CFC 2 F 5 , CF 3 CH═CFCF 2 CF 2 C 2 F 5 , CF 3 CF═CHCF 2 CF 2 C 2 F 5 , CF 3 CF 2 CH═CFCF 2 C 2 F 5 , CF 3 CF 2 CF═CHCF 2 C 2 F 5 , C 2 F 5 CF 2 CF═CHCH 3 , C 2 F 5 CF═CHCH 3 , (CF 3 ) 2 C═CHCH 3 , CF 3 C(CH 3 )═CHCF 3 , CHF 2 CF═CFCF 3 , CH 2 FCF═CFCF 3 , CHF 2 CH═CFCF 3 , CF 3 CH═CFCHF 2 , CHF 2 CF═CFCHF 2 , CH 2 CF═CFCF 3 , CH 2 FCH═CFCF 3 , CF 3 CH═CFCH 2 F, CHF 2 CF═CHCHF 2 , CF 3 CF═CHCH 3 , CF 3 CBr═CFCF 3 , CH 3 CBr═CHCF 3 , CF 3 CBr═CHCH 3 , CF 3 CF═CBrCF 2 CF 3 , E-CHF 2 CBr═CFC 2 F 5 , Z—CHF 2 CBr═CFC 2 F 5 , (CF 3 ) 2 CFCBr═CH 2 , CHBr═CF(CF 2 ) 2 CHF 2 , and (CF 3 ) 2 C═CHCH 2 Br,

and wherein the global warming potential of said blowing agent is less than 100.

12. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the foamable composition comprises a resin selected from the group consisting of polystyrene, polyethylene and polypropylene.

13. The open cell, closed cell or multimodal cell thermoplastic foam of claim 12 , wherein said blowing agent is a hydrofluorocarbon selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , Z—CF 3 CF═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 , and said blowing agent is present in a range of from about 1 to about 30 wt. %, based on the total weight of the resin and blowing agent.

14. The open cell, closed cell or multimodal cell thermoplastic foam of claim 13 , wherein said blowing agent is present in a range of from about 2 to about 20 wt. %, based on the total weight of the resin and blowing agent.

15. The open cell, closed cell or multimodal cell thermoplastic foam of claim 12 , wherein the foamable composition further comprises a nucleating agent.

16. The open cell, closed cell or multimodal cell thermoplastic foam of claim 15 , wherein said nucleating agent is present in range of from about 0.1 to about 10 parts by weight of the nucleating agent per 100 parts by weight of the resin in the foamable composition and the foam is a closed cell foam.

17. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said blowing agent is selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CHCF 2 CF 3 and Z—CF 3 CH═CHCF 2 CF 3 .

18. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said blowing agent is selected from the group consisting of E-CF 3 CH═CHCF 3 , E-CF 3 CH═CHCF 2 CF 3 and Z—CF 3 CH═CHCF 2 CF 3 .

19. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said foam is an closed cell foam having an initial insulation value (R) of at least 4.9/inch (thermal conductivity of 29.5 milliW/mK).

20. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 1 , wherein said polyol is a polyester polyol.

21. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 20 , wherein said polyester polyol is prepared by reacting a carboxylic acid with a polyhydric alcohol.

22. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 20 , wherein said polyester polyol is preblended with the blowing agent to form a stable premix.

23. The open cell, closed cell or multimodal cell polyisocyanate-based foam of claim 22 , wherein the stable premix is mixed to form a mousse-like consistency.

24. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the blowing agent is CF 3 CH═CHCF 3 , CF 3 CH═CHC 2 F 5 , CF 3 CH═CHCF 2 C 2 F 5 , CF 3 CH═CHCF(CF 3 ) 2 , C 2 F 5 CH═CHC 2 F 5 , CF 3 CH═CH(CF 2 ) 3 CF 3 , CF 3 CH═CHCF 2 CF(CF 3 ) 2 , CF 3 CH═CHCF(CF 3 )C 2 F 5 , CF 3 CH═CHC(CF 3 ) 3 , C 2 F 5 CH═CHCF 2 C 2 F 5 , C 2 F 5 CH═CHCF(CF 3 ) 2 , CF 3 CH═CH(CF 2 ) 4 CF 3 , CF 3 CH═CHCF 2 CF 2 CF(CF 3 ) 2 , CF 3 CH═CHC(CF 3 ) 2 C 2 F 5 , C 2 F 5 CH═CH(CF 2 ) 3 CF 3 , C 2 F 5 CH═CHCF 2 CF(CF 3 ) 2 , C 2 F 5 CH═CHCF(CF 3 )C 2 F 5 , C 2 F 5 CH═CHC(CF 3 ) 3 , C 2 F 5 CF 2 CH═CHCF 2 C 2 F 5 , (CF 3 ) 2 CFCH═CHCF(CF 3 ) 2 , C 2 F 5 CH═CHCF(CF 3 ) 2 , CF 3 CH═CH(CF 2 ) 5 CF 3 , CF 3 CH═CHCF(CF 3 )(CF 2 ) 2 C 2 F 5 , CF 3 CH═CHC(CF 3 ) 2 CF 2 C 2 F 5 , C 2 F 5 CH═CH(CF 2 ) 4 CF 3 , C 2 F 5 CH═CHCF 2 CF 2 CF(CF 3 ) 2 , C 2 F 5 CH═CHC(CF 3 ) 2 C 2 F 5 , C 2 F 5 CF 2 CH═CH(CF 2 ) 3 CF 3 , C 2 F 5 CF 2 CH═CHCF 2 CF(CF 3 ) 2 , C 2 F 5 CF 2 CH═CHCF(CF 3 )C 2 F 5 , C 2 F 5 CF 2 CH═CHC(CF 3 ) 3 , (CF 3 ) 2 CFCH═CH(CF 2 ) 3 CF 3 , (CF 3 ) 2 CFCH═CHCF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCH═CHCF(CF 3 )C 2 F 5 , (CF 3 ) 2 CFCH═CHC(CF 3 ) 3 , C 2 F 5 CH═CH(CF 2 ) 5 CF 3 , C 2 F 5 CH═CHCF(CF 3 )(CF 2 ) 2 C 2 F 5 , C 2 F 5 CH═CHC(CF 3 ) 2 CF 2 C 2 F 5 , C 2 F 5 CF 2 CH═CH(CF 2 ) 4 CF 3 , C 2 F 5 CF 2 CH═CHCF 2 CF 2 CF(CF 3 ) 2 , C 2 F 5 CF 2 CH═CHC(CF 3 ) 2 C 2 F 5 , (CF 3 ) 2 CFCH═CH(CF 2 ) 4 CF 3 , (CF 3 ) 2 CFCH═CHCF 2 CF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCH═CHC(CF 3 ) 2 C 2 F 5 , CF 3 (CF 2 ) 3 CH═CH(CF 2 ) 3 CF 3 , CF 3 (CF 2 ) 3 CH═CHCF 2 CF(CF 3 ) 2 , CF 3 (CF 2 ) 3 CH═CHCF(CF 3 )C 2 F 5 , CF 3 (CF 2 ) 3 CH═CHC(CF 3 ) 3 , (CF 3 ) 2 CFCF 2 CH═CHCF 2 CF(CF 3 ) 2 , (CF 3 ) 2 CFCF 2 CH═CHCF(CF 3 )C 2 F 5 , (CF 3 ) 2 CFCF 2 CH═CHC(CF 3 ) 3 , C 2 F 5 CF(CF 3 )CH═CHCF(CF 3 )C 2 F 5 , C 2 F 5 CF(CF 3 )CH═CHC(CF 3 ) 3 , or (CF 3 ) 3 CCH═CHC(CF 3 ) 3 .

25. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the blowing agent is E-CF 3 CH═CHCF 3 , E-CF 3 CH═CHCF 2 CF 3 or Z—CF 3 CH═CHCF 2 CF 3 .

26. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the foam has an overall density of from about 10 to about 500 kg/m 3 .

27. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the foam has an overall density of from about 18 to about 100 kg/m 3 .

28. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the foam is an open cell foam and the blowing agent comprises a hydrofluorocarbon selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 .

29. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the foam is a multi-modal cell foam and the blowing agent comprises a hydrofluorocarbon selected from the group consisting of E-CF 3 CH═CHCF 3 , Z—CF 3 CH═CHCF 3 , E-CF 3 CH═CFCF 3 , Z—CF 3 CH═CFCF 3 , E-CF 3 CH═CHCF 2 CF 3 , Z—CF 3 CH═CHCF 2 CF 3 , E-CF 3 CF═CHCF 2 CF 3 , Z—CF 3 CF═CHCF 2 CF 3 , E-CF 3 CH═CFCF 2 CF 3 , and Z—CF 3 CH═CFCF 2 CF 3 .

30. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein the cell size, excluding voids, is about 200-300 microns (μ).

31. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein said foam has an initial insulation value (R) of at least 2.0/inch (thermal conductivity of 72.1 milliW/mK).

32. The open cell, closed cell or multimodal cell thermoplastic foam of claim 11 , wherein said foam has an initial insulation value (R) of at least 4.0/inch (thermal conductivity of 36 milliW/mK).